Preparation of esters of phosphorus acids

ABSTRACT

HALOGEN-CONTAINING ESTER OF PHOSPHORUS ACIDS ARE PREPARED BY AN IMPROVED PROCESS, WHEREBY THIOL- OR HYDROXYLCONTAINING ORGANIC MATERIALS AND PHOSPHORUS HALIDES ARE REACTED AT SPECIFIED TEMPERATURES IN THE PRESENCE OF AMMONIUM SALTS OF INOGRANIC AND ORGANIC ACIDS THEREBY PROVIDING HIGH YIELDS OF SUBSTANTIALLY PURE ESTERS AND ALLOWING PREPARATION OF SELECTED HALOGEN-CONTAINING MONO- AND DI-ESTERS OF PHOSPHORUS ACIDS HAVING SUBSTANTIALLY NO SIDE REACTANT CONTAMINATION. THE PHOSPHORUS ESTERS ARE USEFUL AS INTERMEDIATES IN THE PREPARATION OF PLASTICIZERS, OIL ADDITIVES AND FUNCTIONAL FLUIDS.

United States Patent Office 3,773,866 Patented Nov. 20, 1973 3,773,866 PREPARATION OF OF PHOSPHORUS Joseph W. Baker and Ignatius Schumacher, St. Louis, Mo., assignors to Monsanto Company, St. Louis, M0. N Drawing. Filed June 24, 1971, Ser. No. 156,563

Int. Cl. C07f 9/08, 9/16 I U.S. Cl. 260-973 17 Claims ABSTRACT OF THE DISCLOSURE Halogen-containing esters of phosphorus acids are prepared by an improved process, whereby thiolor hydroxyl- Containing organic materials and phosphorus halides are reacted at specified temperatures in the presence of ammonium salts of inorganic and organic acids thereby providing high yields of substantially pure esters and allowing preparation of selected halogen-containing monoand di-esters of phosphorus acids having substantially no side reactant contamination. The phosphorus esters are useful as intermediates in the preparation of plasticizers, oil additives and functional fluids.

BACKGROUND OF THE INVENTION This invention relates to a novel process for the preparation of halogen-containing organophosphorus acid esters. More particularly, this invention is concerned with a process comprising an ammonium salt catalyzed reaction of halides of phosphorus and thiolor hydroxyl-containing organic materials.

Numerous methods have been long known for preparing triorganophosphorus esters. One of those methods involves the reaction of a phosphoryl halide and a monohydric organic compound without the use of a catalyst. Such a process is not commercially practical because of the need for lengthy reaction times and the resultant low yields. Another disadvantage of processes of that type is the need for the use of excessive amounts of the monohydric organic compound,

Another known method comprises the addition of certain amines to the aforedescribed reaction mixture to eifect higher yields. Thus, U.S. 1,785,951 discloses the use of certain aromatic amines, e.g., aniline and pyridine, as catalysts for preparing triaryl phosphates from phosphoryl chloride and a phenol at high temperatures. Similarly, U.S. 2,678,940 discloses the use of aromatic primary amines, e.g., aniline, and certain tertiary alkylamines, e.g., trimethylamine, as catalysts for preparing triaryl phosphates from phosphorus trichloride and a phenol. The cited processes, however, are concerned only with the preparation of triaryl phosphates and not with the selective preparation of halogen-containing monoand di-esters of phosphorus acids.

In still other methods, the reaction is catalyzed, so as to produce greater yields, by adding a metal to the reaction mixture, such as copper powder, iron filings, calcium, aluminum or magnesium; or a halide such as aluminum chloride, vanadium chloride, magnesium chloride or boron trifluoride; or a sulfate such as copper sulfate; or an oxide such as magnesium oxide, vanadium oxide or copper oxide.

The employment of such catalyst has several attendant inherent disadvantages, among which are low conversion of the starting materials and lengthy reaction times required for completion of the reaction. As described in U.S. Pats. 2,610,978 and 2,632,018, an insoluble complex forms during the reaction when aluminum chloride is used as a catalyst.

When alcohols are reacted with a phosphoryl halide, either without a catalyst or in the presence of any of the abovementioned catalysts, other than magnesium chloride, undesirable by-products are formed. The by-products contribute difiicult distillation problems, lower yields of the desired product and lower reaction efficiency. A method described in U.S. Pat. 2,410,118 is illustrative of the typical distillation problems encountered. In that method, distillation is difiicult due to the high concentration of salts of various phosphorus acids in the distillation still.

U.S. Pat. 2,868,827 describes the use of titanium tetrachloride as a catalyst for producing organophosphate esters. Disadvantages encountered employing titanium tetrachloride reside in the excessive and lengthy times necessary to obtain desirable yields and the relatively large amounts of the metal halide catalysts required. Further, when the reaction is conducted in the presence of a titanium halide catalyst, recovery of the desired reaction product is a problem. At the completion of the reaction,

it has been found necessary to wash the reaction mixture with a citrate or tartrate solution which forms a complex with the titanium catalyst. The complex is then removed by washing with water followed by drying the remaining product.

Another disadvantage encountered with the employment of many of the aforedescribed catalysts is the need for complicated material-handling procedures for the catalyst.

Additionaly, preparation of organophosphorus esters by the aforedescribed catalyzed reactions restricts the manufacturer in that only one specific type of organophosphorus ester of high purity could be prepared by the reaction. Thus, one could not prepare compounds of high purity such as, for example, cresyl phenyl phosphorochloridate, bromophenyl phenyl phosphorochloridate and the like. By the aforedescribed procedures, only relatively impure triorganophosphorus esters or esters containing the same aryl groups could be prepared, for example, triphenyl phosphate, tricresyl phosphate and the like. Thus, in the preparation of organophosphorus esters by the aforedescribed procedures, the specific organophosphorus esters prepared were contaminated by side reactants which could be only removed by lengthy and diflicult washing and distillation procedures.

U.S. 2,046,031 discloses the addition of anhydrous ammonia upon completion of a phosphoryl chloride-alcohol reaction to prepare phosphorus triesters. The ammonia is added, however, as a hydrogen chloride scavenger, the ammonium chloride formed being separated from the esterification product. Since the ammonia is added subsequent to the esterification reaction, the ammonium chloride formed does not act as a catalyst.

U.S. 2,903,475 discloses reacting phosphonous dichlorides or phosphinous chlorides with alcohols in the presence of anhydrous ammonia which removes formed hydrogen chloride. The preparation of trivalent phosphonites and phosphinites does not necessitate use of a catalyst. Since the alkyl phosphonite or alkyl phosphinite cleaves in the presence of hydrogen chloride, a scavenger such as ammonia is required.

U.S. 2,903,477 discloses the preparation of esters of alcohols and carboxylic acids or anhydrides using sulfuric acid as catalyst. The reaction is carried out in the presence of ammonium ion, added in the form of ammonium salts, in order to inhibit discoloration of the product ester.

Similarly, U.S. 3,151,166 discloses the use of ammonium salts as color stabilizers in the preparation of ethanolamines from ethylene oxide and ammonia.

U.S. 3,155,710 discloses the preparation of phosphate esters, by reaction of phosphoryl halides and alcohols, in the presence of vanadium compounds, such as vanadium halides, ammonium vanadates and vanadium oxides, as catalysts. It has been found, however, that the use of compounds of transition metals of Groups IV-B and V-B of the Perodic Chart of the Elements (pp. 392-393,

3 Handbook of Chemistry and Physics, 35th ed.) as cata lysts for that reaction promotes discoloration of the product, contributes to prolonged reaction time and causes, in general, the same type of problems normally associated with such transition metal catalysts as titanium halides.

Accordingly, the objective of this invention is to provide a novel and improved process for the preparation of halogen-containing monoand diorganophosphorus esters in which the disadvantages of the prior art are eliminated and selective esterification in high yields with substantially no by-product contamination is afforded.

SUMMARY OF THE INVENTION The objective of this invention is accomplished by a novel process, combining a critical combination of catalyst and reaction temperature, for the preparation of halogen-containing organophosphorus acid esters wherein high yields of product are formed with substantially no side reactions and contaminants and whereby step-wise building of the ester is allowed in such a manner that mixed esters are prepared in an easy and economical manner. As an example of the innovative process of this invention, a compound such as chlorophenyl cresyl phosphorochloridate may be conveniently and inexpensively prepared, such preparation being difficult and expensive with known methods now available to the art. Further, mixtures of monoand diorganophosphorus esters may be prepared in the same reaction vessel and separated by distillation precedures without undesirable disproportionation.

The unexpected and surprising aspect of the process of this invention is the fact that while the prior art (U.S. 3,155,710) discloses certain vanadium compounds, e.g., ammonium vanadate, as catalyst for the reaction of, for example, phosphoryl chloride and phenol to prepare triaryl phosphates, it has now been found that such vanadium compounds and compounds closely related thereto, e.g., the ammonium salts of transition metals of Group IV-B and Group V-B of the Periodic Chart of the elements, such as titanium, zirconium, hafnium, niobium and tantalum, are unsuitable as catalysts under the process conditions of the present invention. Thus, the ammonium salts of Group IV-B and Group V-B transition metal acids afford esterification products which are inordinately highly colored and the reaction is subject to the same problems encountered when using the transition metal halides, e.g., titanium tetrachloride, as catalysts.

The novel process of this invention comprises reaction, at specific temperatures, of halides of phosphorus of the formula x Y.. l z.

wherein X represents oxygen or sulfur; Y represents R or R'X wherein R represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclyl or aryl; R represents alkyl or aryl; m. represents when n is 3 and m represents 1 when n is 2; Z represents chloro or bromo; and n represents 2 or 3, with a compound having the formula (II) RXH wherein R" represents aryl and X represents oxygen or sulfur, in the presence of an ammonium salt of an acid.

The reaction sequence involved in the process of this invention proceeds through the following stages, exemplified by the reaction of phenol with phosphoryl chloride:

The phosphorus monoand dihalidates produced are valuable intermediates in the preparation of plasticizers, oil additives and functional fluids and are prepared conveniently by the process of this invention and a high' yield with substatnially no contamination by side reactions.

The catalysts used in the process of this invention may, in general, be any ammonium salt of an inorganic or organic acid which salt is characterized by the presence of a nitrogen atom capable of entering into a liquid complex with the phosphorus moiety of Formula I under the conditions of the present process. Essentially all ammonium salts capable of forming such complex are contemplated as catalysts in this process, with the exception of the ammonium salts of the Group IV-B and Group V-B transition metal acids, i.e., acids of titanium, zirconium, hafnium, vanadium, niobium and tantalum.

The catalyst concentration which is most effective in the process is a function of many variables, but is generally from about 0.001 to 2.0 mole percent based on the phosphorus halide. Preferably, from 0.01 to 0.1 mole percent is considered a practical level. Of course, greater or lesser amounts may be used effectively within the discretion and experience of those skilled in the art. Thus, the following list of ammonium salts is intended merely to illustrate the broad scope of the compounds which are useful as catalysts herein since it would be virtually impossible to specifically list each amonium salt intended. Representative ammonium salts of acids which may be used as catalysts in the process of this invention include the following compounds, which are illustrative only and are not to be considered a limitation since, as defined above, any ammonium salt is suitable providing it is capable of complexing with the phosphorus moiety of Formula I without restriction on the number of carbon atoms in the salt molecule itself, if derived from an organic acid, and without restriction as to the substitutent groups which may be on either the carbon atoms or the nitrogen atoms of the salt compound. Further, there is virtually no limitation on the number of carbon atoms, or other atoms, in the ammonium salt molecule. Accordingly, the only limitation on the size or arrangement of the ammonium salt used is that of practicality and expense. The following list of illustrative compounds is therefore to be read in the light of the above teachings.

Ammonium salts of inorganic acids:

ammonium sulfate ammonium chloride ammonium nitrate ammonium sulfite ammonium acid sulfate ammonium bromide ammonium carbonate ammonium fluoride ammonium nitrite ammonium phosphate ammonium phosphite ammonium silicate ammonium chromate ammonium molybdate ammonium tungstate ammonium manganate ammonium zincate ammonium stannate ammonium stannite ammonium arsenate ammonium antimonate ammonium bismuthate ammonium selenate ammonium chlorate ammonium hypochlorite ammonium hydrobromate ammonium perchlorate ammonium chlorite ammonium aluminum chloride ammonium arsenite ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium Ammonium salts of organic acids:

ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium formate acetate benzenesulfonate chlorgallate propionate butyrate valerate caproate caprate laurate myristate palmitate stearate oxalate malonate succinate adipate sebacate acrylate citraconate linoleate fiuoroacetate chloroacetate chlorobutyrate lactate crotonate glyoxalate acetoacetate benzoate toluate phenylcarbonate gallate cinnamate phthalate sulfamate trimethylacetate S-methyl octanoate arachidate tetracosanate cyclopropanecarboxylate cyclohexanecarboxylate phenylacetate toluate tolylacetate 4-phenylpentanoate naphthoate 2-phenylcyclohexanecarboxylate acenaphthoate biphenylacetate diphenylacetate phenanthroate anthroate Z-furancarboxylate 2-thiophencarboxylate thienylacetate 3-pyridinecarboxylate Z-thenylmalonate indole-Z-carboxylate 3-quino1inecarboxylate 2-dibenzofurylacetate cyclopropylmalonate terephthalate phenyladipate diphenate vinylacetate fumarate 7-octenoate 1-cyclopenteny1carboxylate cinnamate vinylbenzoate 2-furylacrylate propiolate stearolate a-chlorocaproate p-bromobenzoate u-thienylglyoxylate benzoylformate fluorenone-2-carboxylate ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium rial used to prepare a dihalidate phosphorus monoester such as a R phosphorodihalidate. The R phosphorodihalidate may be an intermediate in the preparation of, for example, a monohalidate phosphorus diester such as a di-R' phosphorohalidate. At the same time, however, the R phosphorodihalidate and di-R' phosphorohalidate may be considered monoand di-ester end products of the process of this invention. The phosphorus halides utilized are well known to those skilled in the art. Many are commercially available and all are easily prepared in accordance with the process of this invention. The compounds are encompassed by the scope of Formula I and include, by way of illustration, compounds such as:

Phosphoryl halides:

Thiophosphoryl halides:

R phosphorodihalidates:

R'OIi -Zg O-R' phosphorodihalidothioates:

S-R' phosphorodihalidothioates:

S-R' phosphorodihalidodithioates:

Di-R' phosphorohalidates:

0,0-di-R phosphorohalidothioates:

O,S-di-R' phosphorohalidothioates:

S,S-di-R' phosphorohalidodithioates:

O,S-di-R' phosphorohalidodithioates:

i Zi R S S,S-di-R' phosphorohalidotrithioates:

R-1 Zz R-phosphonothioic dihalides:

R-%Zq Di-R-phosphinic halides:

Rg--Z1 Di-R-phosphinothioic halides:

S Bri -Z1 R'R-phosphonohalidates:

R Oil Zi RR-phosphonohalidothioates:

R'OIII'IZ1 S-R' R-phosphonohalidothioates:

n's-i -zt S-R' R-phosphonohalidodithioates:

In the above formulas, R, R and Z are defined as in Formula I.

As described in Formula I, R represents alkyl, e.g., methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl and eicosyl, whether straight or branched chain in configuration; cycloalkyl, e.g., cyclopropyl, cyclobutyl, cyclopentyl, ethylcyclopropyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, decahydronaphthyl, bicyclohexyl (cyclohexylcyclohexyl), tetradecahydropenanthryl, tricyclohexylmethyl; alkenyl, e.g., ethenyl, propenyl, butenyl, isobutenyl, pentenyl, methylbutenyl, trimethylethenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, hexadecenyl, octadecenyl, eicosenyl; cycloalkenyl, e.g., cyclopropentyl, cyclopentenyl, cyclohexenyl, cyclohexylcyclohexenyl; alkynyl, e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, tridecynyl, octadecynyl, eicosynyl; cycloallgynyl, e.g., 1-cycloden-4-yl; heterocyclic radicals containing oxygen or sulfur in the heterocyclic ring, e.g., thiophenyl,

furanyl, tetrahydrofuranyl, pyranyl, sulfolanyl', aryl, e.g., phenyl, naphthyl, biphenyl, phenanthryl, anthracyl, terphenyl or quaterphenyl; and R represents alkyl or aryl, as described above with reference to R.

R and R may be unsubstituted, as described above, or substituted. It is to be understood that the catalysts of this invention will catalyze the preparation of halogenated organophosphorus esters in accordance with this invention regardless of the type or extent of substitution of the radicals defined as included within R and R above. Thus the radicals represented by R and R may be substituted with any moiety except a carboxyl group or a hydroxyl group which may interfere with the reaction.

The following radicals are illustrative of the substituents which may occur on the groups represented by R and R' of the phosphorus halides and on the organic moieties of ammonium salts formed from organic acids: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl and aryl as described above. Also, halo, e.g., chloro, bromo, fluoro, iodo; alkoxy, e.g., methoxy, propoxy, butoxy, hexoxy, decoxy; cycloalkoxy, e.g., cyclohexoxy, cyclobutoxy; alkenoxy, e.g., propenoxy, cycloalkenoxy, e.g., cyclopentenoxy; aryloxy, e.g., phenoxy, naphthoxy; cyano; nitro; isonitro; aldehyde; ketone, alkoxycarbonyl, e.g., methoxycarbonyl; aryloxycarbonyl, e.g., phenoxycarbonyl; alkylcarbonyloxy, e.g., acetyl; alkoxycarbonyloxy, e.g., acetoxy; arylcarbonyloxy, e.g., benzoyl; alkylthio, e.g., ethylthio; arylthio, e.g., phenylthio, naphthylthio; trihaloalkyl, e.g., trifluoromethyl; alkylsulfinyl, e.g., butylsulfinyl; arylsulfinyl, e.g., phenylsulfinyl: alkylsulfonyl, e.g., propylsulfonyl; arylsulfonyl, e.g., phenylsulfonyl.

Specific phosphorus halides which are encompassed within the scope of this invention, and which may be starting materials and/or desired products, include phosphoryl chloride, phosphoryl bromide, phosphoryl dibromide chloride, thiophosphoryl chloride and bromide, phenyl phosphorodichloridate, p-chlorophenyl phosphorodibromidate, p-nitrophenyl phosphorodichloridate, p-nitrophenyl phosphorodichloridothioate, cresyl phosphorodichloridate, o-methoxyphenyl phosphorodichloridate, nonylphenyl phosphorodichloridate, cumylphenyl phosphorodichloridate, o-biphenyl phosphorodichloridate, naphthyl phosphorodichloridate, isopropylphenyl phosphorodichloridate, tert-butylphenyl phosphorodichloridate, isodecyl phosphorodichloridate, S-phenyl phosphorodichloridothioate, S-p-nitrophenyl phosphorodichloridothioate, S-phenyl phosphorodichloridodithioate, dihenyl phosphorochloridate, dicresyl phosphorochloridate, 0,0-diphenyl phosphorochloridothioate, S,S-diphenyl phosphorobromidodithioate, S,S-dipheny1 phosphorochloridotrithioate, phenylphosphonic dichloride, p-chlorophenylphosphonic dibromide, methylphosphonic dichloride, chloromethylphosphonic dichloride, phenylphosphonothioic dichloride, cresylphosphonothioic dibromide, methylphosphonothioic dichloride, chloromethylphosphonothioic dichloride, butyl phosphorodichloridate, hexyl phosphorodichloridate, octyl phosphorodichloridate, decyl phosphorodichloridate, phenyl phenylphosphonochloridate, p-nitrophenyl phenylphosphonochloridate, cresyl phenylphosphonochloridate, O- phenyl phenylphosphonochloridothioate, S-phenyl phenylphosphonobromidothioate, S-phenyl phenylphosphonochloridodithioate.

The alcohols and thioalcohols embraced by the scope of Formula II include those compounds wherein R" represents aryl groups as defined with respect to R and R of the phosphorus halides. Thus, R" represents phenyl, alkylphenyl, halophenyl, arylphenyl, cycloalkylphenyl, naphthyl, biphenyl, phenanthryl, anthracyl, terphenyl, quaterphenyl, whether substituted or nonsubstituted.

Specific alcohols of the formula R"XH which will illustrate the types of compounds utilized include phenol, o, m, p-cresol, o-ethylphenyl, o, m, p-isopropylphenol, p-tertbutylphenol, p-tert-amylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 2,5-xylenol, 2,3-xyleno1, o, m, p-chlorophenol, p-bromophenol, p-iodophenol, 2,4-dichlorophenol, 2,4,5-

trichlorophenol, pentachlorophenol, o-phenylphenol, pcumylphenol, o cyclohexylphehol, alpha-naphthol, betanaphthol, o-methoxyphenol, p-ethoxyphenol, o-phenoxyphenol, p-nitrophenol, p-trifluoromethylphenol, 2-allylphenol, 2-benzylphenol, vanillin, 4-chloro-3,5-dimethylphenol, 4-chloro-l-naphthol, 2-chloro-4-nitrophenol, 4- cyanophenol, 2,4 di tert-butylphenol, 2,4-dimethoxyphenol, methylsalicylate, 2-fluorophenol, p-hydroxyacetophenone, 4-hydroxybenzaldehyde, thiophenol, p-chlorothiophenol, p-tert-butylthiophenol, thiocresol, thioxylenol, phenylthiophenol, thionaphthol, allylthiophenol.

The compounds of Formulas I and II, described above, are generally known in the art and their methods of preparation are available in standard texts and reference sources.

A preferred class of the compounds of Formula I are those compounds of the formula wherein Y=R or R'O wherein R'=aryl or substituted aryl and R, Z, m and n are defined in Formula I. Representative of this preferred class of compounds are phosphoryl chloride, phosphoryl bromide, phenyl phosphorodichloridate, p-chlorophenyl phosphorodibromidate, p-nitrophenyl phosphorodichloridate, cresyl phosphorodichloridate, o methoxyphenylphosphorodichloridate, nonylphenyl phosphorodichloridate, cumylphenyl phosphorodichloridate, o-biphenyl phosphorodichloridate, naphthyl phosphorodichloridate, isopropylphenyl phosphorodichloridate, tert-butylphenyl phosphorodichloridate, diphenyl pho phorochloridate, dicresyl phosphorochloridate, phenylphosphonic dichloride, p-chlorophenylphosphonic dichloride, methylphosphonic dibromide, chloromethylphosphonic dichloride, phenyl phenylphosphonocloridate, p-nitrophenyl phenylphosphonochloridate, cresyl phenylphosphonochloridate.

A preferred class of the compounds of Formula II are those compounds of the formula R"OH. Representative of this preferred class of compounds are phenol, o, m, pcresol, o-ethylphenol, o, m, p-isopropylphenol, p-tert-butylphenol, p-tert-amylphenol, nonylphenol, xylenol, o, m, pchlorophenol, p-bromophenol, p-iodophenol, dichlorophenol, trichlorophenol, pentachlorophenol, p-cumylphenol, p-nitrophenol, o-cyclohexylphenol, naphthol, methoxyphenol, ethoxyphenol, phenoxyphenol, p-nitrophenol, trifluoromethylphenol, allylphenol, benzylphenol, vanillin, 4 chloro 3,5-dimethylphenol, 4-chloro-1-naphthol, 2-chloro-4-nitrophenol, cyanophenol, di-tert-butylphenol, dimethoxyphenol, methylsalicylate, fiuorophenol.

Especially preferred of this group are phenol, cresol, cumylphenol, nonylphenol, chlorophenol, tert-butylphenol, xylenol, phenylphenol, isopropylphenol and mixtures thereof.

A specialized class of alcohols which are utilized in accordance with this invention are alcohols of the formula O CHa I or phenyl, e.g.

tion with specific temperatures, produces the desired results of this invention. Thus, in the presence of the ammonium catalysts of this invention, the first chlorine of, for example, phosphoryl chloride is replaced at a temperature of from about to about 135 C., preferably 105 C. The second chlorine, i.e., disubstitution, is replaced at a temperature of from about 130 to about 165 C., preferably 150 C. Of course, the specific temperatures for monoand di-substitution will vary with the particular reactants being used, but the comparative differences in the temperatures for the stages of substitution will remain approximately the same.

Accordingly, the combination of specific temperatures for monoand di-substitution of the desired phosphorus halides, together with the catalysts of this invention, enable those skilled in the art to prepare monoor di-organophosphorus esters in selected proportions. Di-organophosphorus esters may be prepared in two stages, with a different alcohol being added at each stage. Similarly, mixtures of esters may be prepared in one reactor. For example, by adding a naphthyl group at the first stage and a chlorophenyl group at the second stage, one may use the same phosphorus halide but merely introduce different appropriate alcohols at the temperature stages set forth to obtain naphthyl chlorophenyl phosphorochloridate and naphthyl phosphorodichloridate. The different compounds may then be recovered separately by methods known in the art. Further, selected proportions of various compounds may be prepared in the same reactor. Thus, if one desires a mixture of phenyl phosphorodichloridate and naphthyl phenyl phosphorochloridate in proportions of 2:1, such selective proportions of the desired products can be made in accordance with the present invention by adding the intended proportion of each appropriate alcohol in the separate stages.

The following examples will serve to illustrate specific embodiments of the concept of this invention but are not to be regarded as restrictive of the scope thereof since it has been found that the process of this invention promotes the reaction between virtually any phosphorus halide and any alcohol as defined herein.

Example 1 To a mixture of 153.4 g. phosphoryl chloride and 2.6 g. ammonium sulfate there is added 94 g. phenol over a one-hour period at a temperature of 105 C. The temperature is raised to 115 C. and held for two hours, cooled and stripped of residual hydrogen chloride and other low boilers. Distillation affords 64.7 percent phenyl phosphorodichloridate and 22.5 percent diphenyl phosphorochloridate.

Example 2 To a mixture of 225 g. phosphoryl chloride and 1 g. ammonium chloride there is added 94 g. phenol over a two-hour period at a temperature of -106 C. The temperature is held at C. for one and one-half hours, allowed to cool to room temperature and stripped. Distillation affords 67.8 percent phenyl phosphorodichloridate and 12.5 percent diphenyl phosphorochloridate.

Example 3 To a mixture of 225 g. phosphoryl chloride and 2 g. ammonium nitrate there is added 94 g. phenol over a two-hour period at a temperature of IDS-107 C. The temperature is held at 107110 C. for two hours, cooled and stripped. Distillation affords 74.5 percent phenyl phosphorodichloridate and 21.1 percent diphenyl phosphorochloridate.

Example 4 To a mixture of 225 g. phosphoryl chloride and 2 g. ammonium acetate there is added 94 g. phenol over a two-hour period at a temperature of 105 C. The temperature is then raised to 110 C. and held for two hours, stripped and allowed to cool to room temperature. Distillation of the reaction mixture afiords 74.2 percent phenyl phosphorodichloridate and 16.7 percent diphenyl phosphorochloridate.

Example 1 2 Example 11 In a reaction pot there is mixed 25 g. phosphoryl chloride and 1.5 g. ammonium cyanate. Addition of 94 g. phenol is started at a temperature of 95 C. and the total To a mixture of 25 g. phosphoryl chloride and 2.4 g. 5 addition is carried out over a period of three hours, durammonium benzenesulfonate there is added 150 g. ping which time the temperature is raised to 105 C. The tert-butylphenol over a period of two hours at a temperareaction is then held at 105-110 C. for an additional one ture of 100 C. The temperature is then raised to 110 and one-half hours, stripped and cooled. Distillation C. and held for two hours, stripped and cooled. Distillaaffords 91.7 percent phenyl phosphorodichloridate and tion of the reaction mixture afiords 94.3 percent p-tert- 5.2 percent diphenyl phosphorochloridate. butylphenyl phosphorodlchlorrdate and 2.5 percent dr-p- Example 12 butylphenyl phosphorochloridate.

E I l 6 To a mrxture of 25 g. phosphoryl chloride and 94 g. Xamp e phenol there is added 18.0 g. ammonium butyrate over To a reaction vessel there is added 113 g. phosphoryl 5 a period of one hour at 105 C. The temperature is then chloride and 0.8 g. ammonium carbonate. Over a period raised to 105-110 C. and held for two hours and the of one hour, a total of 64 g. o-chlorophenol is added and reaction mixture is stripped. Distillation affords 76.7 perthe pot temperature is raised from 100 to 110 C. and cent phenyl phosphorodichloridate and 4.2 percent diheld at 110 C. for one hour and then allowed to gradphenyl phosphorochloridate. ually cool to room temperature. The reaction mixture is 1 13 stripped and there is obtained 108 g. product which Examp e affords, on distillation, 93.7 percent o-chlorophenyl phos- (1) To 315 phosphoryl chloride and 4.0 amphorodrchlorrdate and 7.3 percent dr-o-chlorophenyl phosmonium caproate thaw is added 188 phenol over a Phomchlondatetwo-hour period at a temperature of 105 C. The tem- Example 7 perature is held to 110 C. for two hours and allowed to To a mixture of 225 g. phosphoryl chloride and 0.7 g. cool. T reaction rmxture i p p y p y p ammonium chloride there is added 94 g. phenol over a phol'odlchlorldateone-hour period at 95 C. The temperature is then raised T0 the l'eactlofl mlX'flll'e f there 15 added 138 to 105 C. and held for two hours. The reaction mixture phenol and the emperature 1s ra1sed to 150 C. for is distilled aifording 97 percent phenyl phosphorodi- 9 oll S- The reactlon mixture is allowed to cool and chloridate and 3 percent diphenyl phosphorochloridate. strlpl of p y phospilomdlchlofldate- Dlstlllatloll of the residue affords principally diphenyl phosphorochlo- Example 8 ridate To a reaction vessel there is added 225 g. phosphoryl The following table illustrates further examples of the chloride, 1.0 g. ammonium chloride and g. m-hydroxyreaction of a phosphorus halide and an alcohol or triophenol and the pot temperature is gradually raised to alcohol in the presence of an ammonium catalyst.

TABLE Example Phosphorus halide Alcohol Catalyst 14 Phosphoryl bromide o, m, p-Cresol Ammonium stearate. 15.- Thiophosphoryl chloride o-Ethylphenyl Ammonium aerylate. 16-- P e p o pho o Xylmml Ammonium lactate. 17.. o-Met oxyphenyl phosphorodiehloridate Nonylphenol Ammonium benzoate. 18 Phenylphosphonic dichloride Thiophennl Ammonium phthalate. 19 Ohloromethylphosphonic dibromide o-Methoxyphenol Ammonium naphthoate. 20.. Phenylphosptronothioic dichloride..- Phenoxyphenol Ammonium Z-fiurancarboxylate. 21.. Phenylphosphonic dichloride 4 4'-iospropy1idene dipheuol Ammonium terephthalate. 22.. O-phenyl phosphorochloridothioatefiydroquinone Ammonium oxalate. 23.. S-phenyl phosphorobrornidothioate- Resorcinol Ammonium chloride. 24 p-Ohlorophenyl phosphorodibromidate-- p-Cumylphenol..- Ammoniumae e 25.. Cresyl phosphorodichloridate p tert-Amylphenol Ammonium vinylacetate. 26.. Nonylphenyl phosphorodichloridate. Pentaehlorophenol Ammonium sulfite. 37.. Cumylphenyl phosphorodibromidate-- Phenoxyphenol Ammonium bromide. 38.. Naphthyl phospnorodichloridate p-Bromophenol Ammonium l-eyclopentenylcarboxylate. 29.. Phenylphosphonic dichloride Nitronhenol Ammonium borate. 20 Oumyl phosphorodichlori Nonylnh enol Ammonium formats. 21 Phenyl phosphorodichloridate Fluorophenol Ammonium bicarbonate.

115 C. over three hours. Vacuum is applied and distilla- Example 32 tion of the reaction mixture aifords 92.2 percent m-phenylene bis(diphosphorotetrachloridate) Example 9 Example 10 A mixture of 225 g. phosphoryl chloride, 2.5 g. ammonium phosphate and 114 g. 4,4-isopropylidenediphenol is heated at 100-105 C. for three hours. The reaction mixture is allowed to cool to room temperature and stripped. Distillation atfords 4,4'-isopropylidenediphenyl 7 diphosphorotetrachloridate.

1) To a mixture of 225 g. phosphoryl chloride and 1.5 g. of ammonium chloride there is added 109 g. cresol over a period of two hours at a temperature of C. The temperature is held at 105-110 C. for two hours to aiford cresyl phosphorodichloridate.

(2) The temperature of the reaction mixture obtained in (1) is raised to 135 C. and 109 g. cresol is fed into the reactor over a two hour period. The temperature is held at 150 C. for an additional one and one-half hours to afford dicresyl phosphorochloridate.

Example 33 1) To a mixture of 225 g. phosphoryl chloride and 1.7 g. of ammonium acetate there is added 94 g. phenol over a two-hour period at a temperature of 105-110 C.

The temperature is held for two hours at 110-115 C. to I afford phenyl phosphorodichloridate.

(2) The temperature of the reaction mixture of (1) is raised to C. and 109 g. cresol is fed into the reactor during two hours. The temperature is held at 150 C. for an additional two hours to aiford cresyl phenyl phosphorochloridate.

Example 34 Example '3 1) To a mixture of 225 g. phosphoryl chloride and 1.8 g. ammonium acetate there is added 109 g. cresol over a period of two hours at a temperature of 105 C. The temperature is held at 105-1 C. for two hours to afford cresyl phosphorodichloridate.

(2) The temperature of the reaction mixture obtained in (1) is raised to 135 C. and 94 g. phenol is added during two hours at a temperature of 150 C. and held for an additional two hours to afford cresyl phenyl phosphorochloridate.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The process of preparing organophosphorus esters which comprises reacting a phosphorus halide of the formula wherein X represents oxygen or sulfur; Y represents R or RX; R represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclyl or aryl; R' represents alkyl or aryl; m represents 1 when n=2 and 0 when n=3i n represents 2 or 3; and Z represents chloro or bromo with a compound of the formula R"XH wherein R" represents aryl; and X represents oxygen or sulfur at a temperature of up to about 165 C. in the presence of a catalytic amount of an ammonium salt containing a nitrogen atom capable of forming a complex with the phosphorus moiety of said phosphorus halide.

2. The process of claim 1 wherein R" is selected from the group consisting of phenyl, cresyl, cumylphenyl, nonylphenyl, xylyl, tert-butylphenyl, phenylyl, isopropylphenyl, chlorophenyl and mixtures thereof.

3. A process for preparing an organophosphorusdihalidate which comprises reacting a phosphorus halide according to claim 1 with an approximately equimolar amount of a compound of the formula RXH according to claim 1 at a temperature of about 135 C. in the presence ,of a catalytic amount of an ammonium salt containing a nitrogen atom capable of forming a complex with the phosphorus moiety of said phosphorus halide.

4. The process of claim 3 wherein R" is selected from phenyl, cresyl, cumylphenyl, nonylphenyl, xylyl, tertbutylphenyl, phenylyl, isopropylphenyl, chlorophenyl and mixtures thereof.

5. The process of claim 3 wherein said organophosphorusdihalidate is selected from phenyl phosphorodi- 14 chloridate, phenylyl phosphorodichloridate, cresyl phosphorodichloridate cumylphenyl phosphorodichloridate, tert-butylphenyl phosprorodichloridate, nonylphenyl phosphorodichloridate, xylyl phosphorodichloridate, isopropylphenyl phosphorodichloridate, chlorophenyl phosphorodichloridate and mixtures thereof.

6. A process for preparing a diorganophosphorushalidate which comprises reacting an organophosphorusdihalidate with an approximately equimolar amount of a compound of the formula R"XH according to claim 1 at a temperature of about 165 C. in the presence of a catalytic amount of an ammonium salt containing a nitrogen atom capable of forming a complex with the phosphorus moiety of said organophosphorusdihalidate.

7. The process of claim 6 wherein said diorganophosphorushalidate is selected from nonylphenyl phenyl phosphorochloridate and cumylphenyl phenyl phosphorochloridate and mixtures thereof.

8. A process for preparing organophosphorus esters which comprises reacting, in the presence of a catalytic amount of an ammonium salt containing a nitrogen atom capable of complexing with a phosphorus moiety, (1) a phosphorus halide of claim 1 with an approximately equimolar amount of a first compound of formula R"XH of claim 1 at a temperature of about -135 C. to form an organophosphorusdihalidate, (2) adding an approximately equimolar amount of a second compound of formula R"XH to the reaction product of (1) at a temperature of about -165 C. to form a diorganophosphorushalidate.

9. The process of claim 8 wherein said compound of formula R"XH is selected from the group consisting of phenol, cresol, cumylphenol, nonylphenyl, xylenol, terbutylphenol, phenylphenol, isopropylphenol, chlorophenol and mixtures thereof.

10 The process of preparing organophosphorus esters according to claim 1 which comprises reacting a phosphorus halide of the formula wherein Y represents R or R'O;

R represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclyl or aryl;

R represents aryl;

m represents 1 when n=2 and 0 when n =3;

n represents 2 or 3; and

Z represents chloro or bromo with an approximately n molar amount of a compound of the formula R"XH wherein R represents aryl; and

X represents oxygen or sulfur at a temperature of up to about C. in the presence of a catalytic amount of ammonium salt capable of complexing with a phosphorus moiety.

11. The process of preparing organophosphorus esters according to claim 1 which comprises reacting a phosphorus halide of the formula 15 wherein R represents aryl at a temperature of up to 165 C. in the presence of a catalytic amount of an ammonium salt capable of complexing with a phosphorus moiety.

12. The process of claim 11 wherein R" is selected from phenyl, cresyl, cumylphenyl, nonylphenyl, xylyl, tert-butylphenyl, phenylyl, isopropylphenyl, chlorophenyl and mixtures thereof.

13. The process of claim 11 wherein said ammonium salt is selected from ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium acetate, ammonium benzenesulfonate, ammonium phosphate, ammonium oxalate and ammonium carbonate.

14. The process of preparing organophosphorus esters according to claim 1 which comprises reacting a phosphorus halide of the formula wherein Y represents R or R'O; R represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclyl or aryl; R represents aryl; m represents 1 when n=2 and when n=3; n represents 2 or 3; and Z represents chloro or bromo with an approximately n molar amount of a compound of the formula HO'R"'-OH wherein R" represents isopropylidenediphenylene or phenylene at a temperature of up to about 165 C. in the presence 16 of a catalytic amount of an ammonium salt capable of complexing with a phosphorus moiety.

15. The process of preparing an organophosphorus ester according to claim 11 which comprises reacting phosphoryl chloride with an approximately dimolar amount of phenol at a temperature of up to about 165 C. in the presence of an ammonium salt catalyst capable of complexing with a phosphorus moiety.

16. The process of claim 11 wherein said organophosphorus ester is selected from diphenyl phosphoroehloridate, dicresyl phosphorodichloridate, cumylphenyl phenyl phosphorochloridate, cresyl phenyl phosphorochloridate, nonylphenyl phenyl phosphorochloridate and mixtures thereof.

17. A process for preparing organophosphorus esters which comprises reacting (1) a phosphorus halide of claim 11 with an approximately equimolar amount of a first compound of formula R"OH of claim 11 at a temperature of -135 C., and (2) adding an approximately equimolar amount of a second compound of formula R"OH of claim 11 to the reaction product of (l) at a temperature of -165" C. in the presence of 0.001 to 2.0 mole percent, based on the phosphorus halide, of an ammonium salt containing a nitrogen atom capable of forming a complex with a phosphorus moiety.

References Cited UNITED STATES PATENTS 3,549,730 12/1970 Abadir et al. 260975 ANTON H. SU'ITO, Primary Examiner U.S. Cl. X.R.

3 7' UNITED STATES PATENT OFFICE 7 CERTIFICATE OF CORRECTION Patent No. 3,773,866 7 Dated November 20, 1973 Inventor) Joseph W. Baker and Ignatius 'Schumacher It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 27, "amonium" should read ammonium Column 9, line 57 immediately following the formula H0-R"'-OH insert wherein R'" represents isopropylidenediphenylene,

Column 11, line 5, 1'25" should read 225 -u- Column 11, line l2, delete "'butylphenyl phosphorochloridate" and substitute therefor tert-butylphenyl phosphorochloridate Column 12, line 1 "'25" should read 225 4 Column 12, line :12, "2s" should read 225 In the table bridging Columns 11 and 12, under, the heading "Example" the last five example numbers should be as follows:

"37"-should be 27 "38" should be 28 "29" is correct "20" should be 30 "21" should be 31 In the table bridgingvcol umns l1 and 12,-under the heading "Alcohol" the entry "4,4'-iospropy1idenediphenol" should read 4,4'- isopropylidene diphenol I In the table bridging Columns 11- 'and- 12, under the heading "Catalyst" the entry "Ammonium 2-flurancarboxyl.ate" should read Ammonium 2-furancarboxylate Column 14, line 33 (Claim 9) "ter-" should read tert- (5/69) UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION 3,773,866 n November" 20,- 1973 Patent No.

Joseph W. Baker and Ignatius Schumacher Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected ae shown below:

Page 2 Column 14, I line 65' (Claim 11) immediately following the formula, insert wherein Column s, line 3 3,"R" should read R'" Signed and seeled this ll 'th day of Maj 19714.).

I (SEAL) Attest:

EDWARD I LFLE'ICHEfh-JR. C. MARSHALL DANN Abbe sting Officer I v v Commissioner of Patents 

